Ag/P-g-C3N4复合材料可见光催化降解双酚AF的机理研究

利用简单的热聚合及原位沉淀法制备了一系列不同质量比(1%～10%)的Ag/P-g-C_3N_4复合材料,采用XRD、SEM、TEM、UV-Vis DRS、FTIR、BET和XPS等表征手段对复合材料的形貌结构、光学特性和化学组成进行了表征.利用合成材料光催化降解双酚AF(BPAF),研究了溶液初始pH、溶解性有机质(DOM)对BPAF降解的影响,并对光催化降解机理进行了探讨.结果表明,在pH=7时,5%Ag/P-g-C_3N_4表现出最强的光催化性能,其在90 min内对BPAF的降解率达到100%.DOM在低浓度(0.5 mg·L~(-1))时促进了BPAF的光降解,而在高浓度时(2～10 mg·L~(-1))抑制了BPAF的光降解.活性基团捕获实验结果表明,在Ag/P-g-C_3N_4降解BPAF过程中,h~+和·OH起主要的作用,直接参与了BPAF的降解.相对于P-g-C_3N_4,Ag/P-g-C_3N_4光催化性能的增强主要是因为Ag的负载促进了e~-和h~+的分离,同时Ag单质的SPR效应提高了复合材料对可见光的吸收率,延长了光生载流子的寿命.     

可见光驱动微生物光电化学池处理剩余污泥同步产氢

氢气是一种理想的清洁能源.太阳能驱动的微生物光电化学池(Microbial photoelectrochemical cell, MPEC)因可同时实现废物处理与自发产氢而受到人们的关注.本文以剩余污泥为底物,构建了一种由无定型硫化钼改性硅纳米线(MoS_3/SiNWs)光阴极和生物阳极组成的MPEC系统,研究了3组MPEC在不同的酸性阴极液pH和外加电压条件下的产氢及污泥减量效果.研究结果表明,MPEC在阴极液pH为1和3的条件下均能在无外加电压下自发产氢;pH=1的MPEC-1实验中平均产氢速率为(0.66±0.02) mL·h~(-1),约是pH=3的MPEC-2实验平均产氢速率的1.5倍,但阴极过酸的条件限制了其实际应用; pH为3、外加0.2 V电压的MPEC-3与MPEC-2相比,产氢周期由15 h增加到40 h,平均产氢速率由(0.44±0.05) mL·h~(-1)提高到(0.52±0.04) mL·h~(-1),污泥TCOD、SCOD、TSS、VSS的降解率分别可达53.96%、70.18%、38.21%和61.76%.可见本文构建的MPEC系统是一种有前景的利用太阳能进行废物处理和资源化的新技术.     

三维有序介孔铈钴铜催化剂的制备及其降解邻二甲苯的机制

以PMMA为模板,通过聚乙二醇(PEG400)和柠檬酸辅助的溶胶凝胶法制备三维有序介孔铈钴铜(3DOM 3C)催化剂,应用BET、SEM、XRD和XPS等对不同煅烧温度的3DOM 3C催化剂进行表征分析,研究了催化剂活性及其影响因素,并利用FT-IR和GC-MS对降解产物进行分析,推测出催化降解邻二甲苯的机理.结果表明,煅烧温度500℃时制备的3DOM 3C催化剂表面具有三维介孔结构,且分散均匀,表面的晶体氧化物最少,存在大量的Cu~(2+)、Ce~(3+)和表面氧,催化剂表面存在更多的固溶体、表面活性位点和氧空位,有利于提高催化活性.在邻二甲苯初始浓度600 ppm、空速16000 h~(-1)、50%O_2条件下,煅烧温度500℃时制备的3DOM 3C催化效果最佳,在260℃时,3DOM 3C催化剂对邻二甲苯的转化率达98%,T_(90)为250℃. 3DOM 3C对邻二甲苯的转化率随着初始浓度、空速和相对湿度的升高而呈下降趋势,随着O_2含量的增加而增加.气流中混入150 ppm的乙酸乙酯能够提高邻二甲苯的转化率,提高其低温催化性能.邻二甲苯催化反应后催化剂表面的O—H、■、C—H和金属—氧键都相应的减少,降解中间产物主要有邻甲基苯甲醛和邻甲基苯甲酸.邻二甲苯降解反应涉及Mars Van Krevelen机理(MVK),先被氧化成邻甲基苯甲醛,再进一步氧化成邻甲基苯甲酸,最终生成CO_2和H_2O.     

铁碳促进O3/H2O2体系深度处理准好氧矿化垃圾床渗滤液尾水中难降解有机物

构建了铁碳-O_3/H_2O_2体系降解矿化垃圾床渗滤液尾水中有机物,并考察了体系O_3、铁碳及H_2O_2投加量、初始pH值和反应时间对铁碳-O_3/H_2O_2体系处理渗滤液尾水的影响.结果表明,在铁碳投加量为3 g·L~(-1),O_3投加量为9.798 mg·min~(-1),H_2O_2投加量为2 mL·L~(-1),初始pH值为3的条件下,反应10 min后,渗滤液尾水的COD和UV_(245)分别从711.96 mg·L~(-1)、0.19下降至295.04 mg·L~(-1)、0.10.类比实验结果表明,铁碳-O_3/H_2O_2体系对渗滤液尾水有机物具有较高的去除率,且可生化性得到提高(BOD/COD从0.04增加至0.40).紫外-可见和三维荧光光谱显示,废水中难降解有机物转化为小分子有机化合物且腐殖质的分子缩合度降低.最后,采用SEM-EDS、XRD和XPS技术对铁碳-O_3/H_2O_2体系的反应机理进行了解析,发现铁碳-O_3/H_2O_2反应的机理为铁碳微电解反应、铁氧化物-H_2O_2非均相芬顿反应、O_3/H_2O_2、铁碳-O_3非均相的高级氧化作用和铁基胶体对有机物的吸附沉淀作用.研究表明,铁碳-O_3/H_2O_2体系是一种能够有效去除矿化垃圾床渗滤液尾水中难降解有机物的方法.     

高分散MnOx/SAPO-34催化剂的制备及其低温NH3选择性催化还原NO性能

采用改进的溶胶-凝胶法制备一系列MnO_x/SAPO-34催化剂,考察了各制备参数对催化剂的结构及其低温氨选择性催化还原(NH_3-SCR)脱硝性能的影响,并通过X射线衍射、N_2吸附-脱附、透射电镜、X射线光电子能谱、NH_3程序升温脱附等手段对催化剂进行表征.结果表明,当制备参数为n(乙醇)/n(Mn)=15,n(H_2O)/n(Mn)=20,n(柠檬酸)/n(Mn)=1,Mn负载量为15%(质量分数),催化剂焙烧温度为350℃时,制备的高分散15%-MnO_x/SAPO-34-350℃催化剂具有最佳的低温SCR活性,在空速为45000 h~(-1)的条件下,且反应温度在120～240℃范围时均保持90%以上的NO转化率和接近100%的N_2选择性.MnO_x纳米颗粒高度分散在SAPO-34载体表面,平均粒径约为5.46 nm,纳米颗粒的表面效应使得该催化剂具备较大的比表面积,暴露出大量的活性位点和高活性的MnO_2(110)晶面,同时,高Mn~(4+)比例和更多的化学吸附氧以及适宜的表面酸强度和酸量也是15%-MnO_x/SAPO-34-350℃催化剂呈现最佳低温SCR活性的重要原因.     

Efficient degradation of organic pollutants by S-NaTaO3/biochar under visible light and the photocatalytic performance of a permonosulfate-based dual-effect catalytic system

Removing large concentrations of organic pollutants from water efficiently and quickly under visible light is essential to developing photocatalytic technology and improving solar energy efficiency. This study used a simple hydrothermal method to prepare a non-metallic, S-doped NaTaO₃ (S-NTO) photocatalyst, which was then loaded onto biochar (BC) to form a S-NTO/BC composite photocatalyst. After uniform loading onto BC, the S-NTO particles transformed from cubic to spherical. The photogenerated electron-hole pair recombination probability of the composite photocatalyst was significantly lower than those of the NTO particles. The light absorption range of the catalyst was effectively widened from 310 nm UV region to visible region. In addition, a dual-effect catalytic system was constructed by introducing peroxymonosulfate (PMS) into the environment of the pollution to be degraded. The Rhodamine B, Methyl Orange, Acid Orange 7, tetracycline, and ciprofloxacin degradation efficiency at 40 mg/L reached 99.6%, 99.2%, 84.5%, 67.1%, and 70.7%, respectively, after irradiation by a 40 W lamps for 90 min. The high-efficiency visible-light catalytic activity of the dual-effect catalytic system was attributed to doping with non-metallic sulfur and loading of catalysts onto BC. The development of this dual-effect catalytic system provides new ideas for quickly and efficiently solving the problem of high-concentration organic pollution in aqueous environments, rationally and fully utilizing solar energy, and expanding the application of photocatalytic technology to practice.     

Component regulation in novel La-Co-O-C composite catalyst for boosted redox reactions and enhanced thermal stability in methane combustion

A novel La-Co-O-C (LC-C) composites were prepared via a facile co-hydrothermal route with oxides and glycerol and further optimized for methane catalytic activity and thermal stability via component regulation. It was demonstrated that Co₃O₄ phase was the main component in regulation. The combined results of X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption of oxygen (O₂-TPD), temperature-programmed reduction of hydrogen (H₂-TPR), temperature-programmed desorption of ammonia/carbon dioxide (NH₃/CO₂-TPD) revealed that component regulation led to more oxygen vacancies and exposure of surface Co²⁺, lower surface basicity and optimized acidity, which were beneficial for adsorption of active oxygen species and activation of methane molecules, resulting in the excellent catalytic oxidation performance. Especially, the (3.5)LC-C (3.5 is Co-to-La molar ratio) showed the optimum activity and the T₅₀ and T₉₀ (the temperature at which the CH₄ conversion rate was 50% and 90%, respectively) were 318 and 367°C, respectively. Using theoretical calculations and in situ diffuse reflection infrared Fourier transform spectroscopy characterization, it was also found that the catalytic mechanism changes from the “Rideal-Eley” mechanism to the “Two-term” mechanism depending on the temperature windows in which the reaction takes place. Besides, the use of the “Flynn-Wall-Ozawa” model in thermoanalytical kinetics revealed that component regulation simultaneously optimized the decomposition activation energy, further expanding the application scope of carbon-containing composites.     

Promotional catalytic activity and reaction mechanism of Ag-modified Ce0.6Zr0.4O2 catalyst for catalytic oxidation of ammonia

Ce_1-xZr_xO₂ composite oxides (molar, x = 0-1.0, interval of 0.2) were prepared by a cetyltrimethylammonium bromide-assisted precipitation method. The enhancement of silver-species modification and catalytic mechanism of adsorption-transformation-desorption process were investigated over the Ag-impregnated catalysts for low-temperature selective catalytic oxidation of ammonia (NH₃-SCO). The optimal 5 wt.% Ag/Ce_0.6Zr_0.4O₂ catalyst presented good NH₃-SCO performance with >90% NH₃ conversion at temperature (T) ≥ 250°C and 89% N₂ selectivity. Despite the irregular block shape and underdeveloped specific surface area (∼60 m²/g), the naked and Ag-modified Ce_0.6Zr_0.4O₂ solid solution still obtained highly dispersed distribution of surface elements analyzed by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) (mapping), N₂ adsorption-desorption test and X-ray diffraction (XRD). H₂ temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) results indicated that Ag-modification enhanced the mobility and activation of oxygen-species leading to a promotion on CeO₂ reducibility and synergistic Ag⁰/Ag⁺ and Ce⁴⁺/Ce³⁺ redox cycles. Besides, Ag⁺/Ag₂O clusters could facilitate the formation of surface oxygen vacancies that was beneficial to the adsorption and activation of ammonia. NH₃-temperature programmed desorption (NH₃-TPD) showed more adsorption-desorption capacity to ammonia were provided by physical, weak- and medium-strong acid sites. Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments revealed the activation of ammonia might be the control step of NH₃-SCO procedure, during which NH₃ dehydrogenation derived from NH_x-species and also internal selective catalytic reduction (i-SCR) reactions were proposed.     

In-situ-reduced synthesis of cyano group modified g-C3N4/CaCO3 composite with highly enhanced photocatalytic activity for nicotine elimination

Graphite carbon nitride has many excellent properties as a two-dimensional semiconductor material so that it has a wide application prospect in the field of photocatalysis. However, the traditional problems such as high recombination rate of photogenerated carriers limit its application. In this work, we introduce nitrogen deficiency into g-C₃N₄ to solve this problem a simple and safe in-situ reduction method. g-C₃N₄/CaCO₃ was obtained by a simple and safe one-step calcination method with industrial-grade micron particles CaCO₃. Cyano group modification was in-situ reduced during the thermal polymerization process, which would change the internal electronic structure of g-C₃N₄. The successful combination of g-C₃N₄ and CaCO₃ and the introduction of cyanide have been proved by Fourier transform infrared spectroscopy and X-ray photoelectron spectrometer. The formation of the cyano group, an electron-absorbing group, promotes the effective separation of photogenic electron hole pairs and inhibits the recombination of photogenic carriers. These advantages result in the generation of more •O₂⁻ and ¹O₂ in the catalytic system, which increases the photocatalytic efficiency of nicotine degradation by ten times. Furthermore, the degradation process of nicotine has been studied in this work to provide a basis for the degradation of nicotine organic pollutants in the air.     

浅谈3G在防震减灾中的应用

通过对比第一代和第二代与第三代移动通信系统的特点,总结出第三代移动通信的优点,并将其优点应用到防震救灾事业中,改善防震减灾系统的设计,使防震减灾步入一个崭新的3G阶段,提高防震减灾工作的有效性和实用性.